CN1955304A - Method for producing 1,3-propylene of using glycerol anaerobic fermentation - Google Patents
Method for producing 1,3-propylene of using glycerol anaerobic fermentation Download PDFInfo
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- CN1955304A CN1955304A CN 200510047540 CN200510047540A CN1955304A CN 1955304 A CN1955304 A CN 1955304A CN 200510047540 CN200510047540 CN 200510047540 CN 200510047540 A CN200510047540 A CN 200510047540A CN 1955304 A CN1955304 A CN 1955304A
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Abstract
This invention provides a promoting cell synthesizing trimethylene glycol method by adding organic intermediary metabolism molecule, and it belongs to trimethylene glycol biosynthesize technology field. Aim at the problem of low transformation efficiency of single cell using glycerine anaerobic fermentation in present technology, this invention realizes ideal flux distribution of substrate and product during the process of trimethylene glycol fermentation, which makes high effect trimethylene glycol fermentation into reality. The invention breaks through the bottleneck of low trimethylene glycol transformation efficiency using glycerine biosynthesis, which improves the transformation efficiency of substrate, shortens fermenting time and cuts down the cost.
Description
Technical field
The invention belongs to technical field of bioengineering, relate to that to utilize single microorganism be 1 with the bio-transformation of fermentable glycerine carbon source, the method for ammediol.
Background technology
As everyone knows, 1, ammediol is important chemical material and medicine intermediate, is a kind of in producing trevira and the monomer that has potential using value in making polyurethane and ring compound.
The industrial chemical synthesis of mainly taking carries out 1, the production of ammediol at present.Having known has a variety of chemistry routes can produce 1, ammediol, but the chemical method by product is many, and product separation is purified difficult, and production cost is corresponding higher.By contrast, biotransformation method produces 1, and ammediol utilizes characteristics such as renewable resource, environmental pollution are little more and more to be subject to people's attention with it.
Produce 1 at present, the microbial method of ammediol is broadly divided into three classes: the one, and be 1 with intestinal bacteria with the glycerine disproportionation, ammediol (USP5254467 and EP0373230 A1); The 2nd, be that substrate produces 1 with genetic engineering bacterium, ammediol (PCT/US 96/-6705, USP5599689, WO 96/35796, WO 9821340 and WO 9821339) with glucose; The 3rd, with production glycerine and 1, two strain bacterium mixed culture (USP 5599689) of ammediol.These methods respectively have relative merits: the transformation efficiency of first method and production concentration are all higher, but glycerine is on the high side, influence 1, the production cost of ammediol; Second method can reduce raw materials cost, but the throughput of genetic engineering bacterium and stability thereof are also not ideal; The third method helps to reduce the time of two-step fermentation, but, under aerobic condition, grow usually as producing glycerol stock, and produce 1 because the growth conditions of two kinds of bacterium is not quite similar, the ammediol bacterium is growth under anaerobic usually, therefore is difficult to obtain comparatively ideal effect.
With regard to present circumstances, transformation of glycerol 1, the technology of ammediol are the most ripe, and effect is also best.More satisfactory method is to utilize glycerine to do substrate, is fermented bacterium with klebsiella (Klebsieblla penumoniae), Fei Shi citric acid fungus (Citrobacter freandii) and clostridium butyricum anaerobism such as (Clostridiumbutyricum) or facultative anaerobe.These fermented bacteriums have solved the problem of substrate and product high density tolerance difference.They utilize glycerine to carry out anaerobism or amphimicrobian metabolism and produce 1, and ammediol is all undertaken by oxidation and two branch roads of reduction, and the energy charge (being provided by ATP) by organism between two branch roads and hydrogen lotus are (by NADH
2Provide) keep metabolic flux and distribute.The oxidative pathway key step: 1) (this enzyme is an anaerase to glycerine, with NAD for Glycerol dehydrogenase, GDH) catalysis generation 2-pyruvic alcohol (DHA) through glycerol dehydrogenase
+Be coenzyme, be subjected to the influence of the hydrogen lotus level of system; 2) DHA generates phosphodihydroxyacetone (DHAP) under the effect of ATP and 2-pyruvic alcohol kinases (Dihydroxyacetone kinase); 3) pyruvic acid is produced in the further metabolism of DHAP.Pyruvic acid is an important intermediate product very in the metabolic process, and its further metabolism is various small molecules products, as acetate, lactic acid, ethanol, methyl alcohol etc., produces thalli growth simultaneously and produces necessary NADH
2And ATP, these small molecule by-products carry out anaerobically fermenting again.Along with the carrying out of fermentation, their accumulation has greatly influenced the ability of thalli growth and production.The reduction approach have two the step enzyme reactions: 1) glycerol dehydratase (Glycerol dehydrogenase, GDHt) (being that reaction system is in lower redox potential) is intermediate product 3-hydroxy propanal (3-HPA) with transformation of glycerol under the anaerobic conditions; 2) at NADH
2Exist down, 3-HPA is through 1, and the ammediol desaturase (1,3-Propanediol dehydrogenase, PDDH) catalysis generates 1, ammediol.Oxidative pathway provides enough NADH for the reduction approach
2
Compare with chemical synthesis, present transformation of glycerol method exists that production concentration is low, the production cycle is long and problem such as glycerol conversion yield is low, causes lacking the market competitiveness and can't realize industrial applications.Wherein, glycerol conversion yield is low is an important factor that causes its production cost high.Solving the low problem of glycerol conversion yield at present mainly is to adopt the method for Double bottom thing cooperative fermentation, be that cosubstrate carries out two sections integrated fermentative production 1 of Double bottom thing with glucose among the CN 1434122A for example, ammediol, glycerol conversion yield increases, but 1, the output of ammediol is not high, a little less than thalline utilizes glycerol fermentation late growing stage ability.People such as Sylvie study by the ratio of glucose and glycerine in the adjusting mixed culture medium, though find that also adding these cosubstrates can improve glycerol conversion yield, glycerine is to 1, and the metabolic flux of ammediol is little, and application prospect is very not bright and clear.Utilize 1 among the CN 1446919A, need to consume the characteristic of a certain amount of reducing equivalent in the ammediol biosynthetic process, add an amount of reductive agent, strengthen reducing equivalent (NADH in the thalline at fermention medium or in anaerobic fermentation process
2) accumulation, promote substrate glycerine along the metabolism of reduction approach, to improve 1, the synthetic concentration and the transformation efficiency of ammediol.The glycerol conversion yield of this method and fermentation efficiency increase rate are limited.
Above-mentioned the whole bag of tricks does not all improve fermentation efficiency well.Various documents and materials show, add a small amount of multiple organic substance and carry out effective metabolism report is not also arranged.
Summary of the invention
Utilize the low problem of glycerine anaerobically fermenting transformation efficiency at single thalline, the invention provides a kind of glycerol fermentation synthetic 1, improving one's methods of ammediol, promptly in fermention medium or anaerobic fermentation process, add an amount of organic intermediary metabolism molecule, the later metabolic process of pyruvic acid in the oxidation reinforced metabolism branch road, the follow-up metabolism stream of pyruvic acid is mainly carried out towards the TCA circulation, thereby in offering glycerine reduction branch road, form 1, during ammediol required NADH the time, weaken thalline more generation acetate under anaerobic conditions, lactic acid, ethanol, the trend of metabolism such as methyl alcohol small molecule by-product stream, improve the bacterial metabolism process, increase the intercoupling property of thalli growth and production, improve fermentation efficiency.
Technical solution of the present invention is: preparation is used to cultivate the fermention medium of Cray Bai Shi bacillus, and in above-mentioned substratum, insert Cray Bai Shi bacillus seed culture fluid, carry out anaerobically fermenting to synthesize 1, ammediol, it is characterized in that, in described fermention medium, add organic intermediary metabolism molecule.Described organic intermediary metabolism molecule is selected from one or more in citric acid, succsinic acid, fumaric acid or the oxysuccinic acid, and the concentration in fermention medium is 0.1g/L～1.0g/L.
The another kind of scheme of the present invention is: preparation is used to cultivate the fermention medium of Cray Bai Shi bacillus, and in above-mentioned substratum, insert Cray Bai Shi bacillus seed culture fluid, carry out anaerobically fermenting with synthetic 1, ammediol, it is characterized in that, anaerobically fermenting is synthetic 1 carrying out, and in the process of ammediol, adds organic intermediary metabolism molecule in the exponential phase of thalli growth.Described organic intermediary metabolism molecule is selected from one or more in citric acid, succsinic acid, fumaric acid or the oxysuccinic acid, and its concentration in fermented liquid is 0.1g/L～1.0g/L.
The inventive method has realized 1 by adding organic intermediary metabolism molecule, ideal Flux Distribution between substrate and product in the ammediol fermenting process, and then realize efficiently 1, the ammediol fermentation.The benefit of this method is to have simplified greatly microbial fermentation and produces 1, the technological process of ammediol, break through the glycerine biological process and produced 1, the bottleneck that the ammediol glycerol conversion yield is low, improve substrate conversion efficiency, shortened fermentation time, thereby reduced production cost, produce 1 for microorganism utilizes the glycerol fermentation method, the industrialization of ammediol is laid a good foundation.
Embodiment
The present invention program's embodiment is carried out according to the step of prior art, and the present invention program's one concrete steps are:
(1) medium preparation: must contain the required nutritive ingredient of thalli growth in the minimum medium, carbon source is a glycerine, nitrogenous source is yeast extract paste or ammonium salt, also contain negatively charged ion such as positively charged ions such as sodium, potassium, ammonium, magnesium, calcium and phosphate radical, sulfate radical, chlorion in addition, and trace elements such as zinc, iron, nickel, copper, cobalt, boron and molybdenum.Add an amount of organic intermediary metabolism molecule in addition in substratum, described organic intermediary metabolism molecule is selected from one or more in citric acid, succsinic acid, fumaric acid or the oxysuccinic acid, and it adds concentration is 0.1g/L～1.0g/L.Substratum sterilization under 121 ℃, 0.1MPa was used in 20 minutes.
(2) seed culture: shake in the bottle and cultivate, temperature is 32 ℃～42 ℃, and rotating speed is 100～200 rev/mins, and incubation time is 15～30 hours, and nitrogen feeding amount is 0.1～1 liter/minute.
(3) fermentation culture: cultivate in the fermentor tank, inoculum size 10v%～15v%, rotating speed are 100～300 rev/mins, and temperature is controlled at 32 ℃～42 ℃, and pH is controlled between 5.0～9.0.Fermentor tank keeps anaerobic condition, and nitrogen feeding amount is 2～4vvm.
Fermentation mode can be that batch fermentation, batch formula stream add fermentation or continuously ferments.Intermittently or batch formula stream to add fermentation time be 20～60 hours, the stable state time of continuously fermenting is 30～40 hours, in the fermented liquid 1, the ultimate density of ammediol can reach 20g/L～70g/L, the molar yield of substrate can reach 50%～80%.
During batch fermentation in the substratum concentration of glycerine be 15g/L～30g/L, the glycerol concentration of adding when batch formula stream adds fermentation is 70g/L～90g/L, glycerol concentration is 15g/L～30g/L in the substratum that continuously ferments.Initial glycerol concentration with 20g/L when continuously fermenting carries out the one-level cultivation, and dense above behind the 2.0g/L up to bacterium, the beginning Continuous Flow adds fresh substratum and carries out the stable state fermenting process, and thinning ratio is 0.5～1.0h
-1
The present invention program two implementation step is: change the organic intermediary metabolism molecule that adds in the scheme one into the exponential phase adding of thalli growth during the fermentation, adding concentration is constant.
The present invention can also add an amount of organic intermediary metabolism molecule simultaneously in seed culture medium, described organic intermediary metabolism molecule is selected from one or more in citric acid, succsinic acid, fumaric acid or the oxysuccinic acid, and the concentration in seed culture medium is 0.1g/L～1.0g/L.
Except adding an amount of organic intermediary metabolism molecule, the present invention can also be in fermention medium or anaerobic fermentation process the exponential phase of thalli growth add proper vitamin C and/or vitamin-E reductive agent, add-on is 40mg/L～150mg/L.
By the following examples the present invention program is further elaborated.All adopt batch formula stream to add fermentation mode among comparative example of the present invention and the embodiment.
Embodiment 1
Used bacterial classification is Cray Bai Shi bacillus (Klebsiella pneumoniae) in the embodiment of the invention, from Sinopec Fushun Petrochemical Research Institute patent bacterial classification, bacterial classification is in Chinese common micro-organisms DSMZ (CGMCC), culture presevation number: 0798.
Substratum divides two kinds of seed culture medium and fermention mediums:
Seed culture medium is formed: (1L)
K
2HPO
4： 34g KH
2PO
4： 13g
(NH)
4SO
4： 6g MgSO
4·7H
2O：0.2g
CaCl
2·H
2O：0.02g CaCO
3： 2.0g
Yeast extract paste: 1.0g glycerine: 60g
Fe
2+Solution: 2.0mL trace element solution I:1.0mL
Fe wherein
2+Solution: (FeSO
45g/L HCl (37%) 4.0mL)
Trace element solution I forms (mg/L):
MgSO
4·4H
2O： 100mg/L ZnCl
2： 70mg/L
Na
2MoO
4·2H
2O：35mg/L H
3BO
3： 60mg/L
CoCl
2·6H
2O： 200mg/L CuSO
4·5H
2O： 29.28mg/L
NiCl
2·6H
2O： 25mg/L 37％HCl： 0.9mL
Fermention medium is formed (1L)
NH
4Cl： 5.35g KCl： 0.75g
NaH
2PO
4·H
2O：1.38g Na
2SO
4： 0.28g
MgCl
2·6H
2O： 0.26g CaCl
2·H
2O：0.0029g
Citric acid: 0.2g yeast extract paste: 1.0g
Bubble enemy (rare): 0.1mL glycerine: 40.0g
Trace element solution II:5mL
Wherein trace element solution II forms (mg/L):
FeCl
3·6H
2O：5.0mg/L Na
2MoO
4·2H
2O：0.005mg/L
ZnCl
2·6H
2O：0.68mg/L MnCl
2·4H
2O： 0.17mg/L
H
3BO
3： 0.06mg/L CoCl
2·6H
2O： 0.47mg/L
CuCl
2·2H
2O：0.17mg/L 37％HCl：1.0mL
Seed and fermention medium will be pH regulator 7.0 all before sterilization.
Fermenting process divides seed culture and two steps of fermentation culture.
Seed culture is shaken in the bottle at baffled triangle of 500mL and is carried out, liquid amount is 200mL, bottleneck seals with soft rubber ball, and on bottle stopper, have two air inlet/outlets, inlet mouth feeds the bottom by conduit, and feeding nitrogen flow is 0.1～1 liter/minute, and shaking speed is 150 rev/mins, culture temperature is 37 ℃, and incubation time is 20 hours.
Fermentation culture is carried out in automatic fermenter, and fermentation volume is 6L, and temperature and invariablenes turning speed are at 37 ℃ and 150 rev/mins, and the nitrogen air flow is 3vvm, regulates pH with the sodium hydroxide of 5mol/L and is controlled at 7.0, fermentation time 40～60 hours.
Concrete fermenting experiment result is as follows: initial glycerol concentration is 20g/L, and organic intermediary metabolism molecule initial concentration is 0.2g/L, and glycerol concentration maintains～40g/L in the anaerobic fermentation process fully.The time of this fermentation period is 40 hours, finally records in the fermented liquid 1, and the concentration of ammediol is 54.5g/L, and the glycerine molar yield is 52.1%.
Comparative example 1 is the fermenting experiment that carries out when not adding organic acid.
Embodiment 2-5 is respectively and adds the fermenting experiment that different organic acids and different concns organic acid carry out, and the experimental result of comparative example 1 and embodiment 1-5 gained is listed in table 1.
Embodiment 6-10 adds organic acid at the exponential phase (about 4-12 hour) of thalli growth during the fermentation, does not add organic acid in fermention medium, and other condition is constant, and experimental result is listed in table 2.
By table 1 as seen, in fermention medium, add organic intermediary metabolism molecule of 0.1g/L～1.0g/L, keeping 1, under the suitable situation of the concentration of ammediol, can make the molar yield of glycerine improve 2.0 to 15.4 percentage points.Table 2 is demonstration then, and the exponential phase of thalli growth adds organic intermediary metabolism molecule of 0.1g/L～1.0g/L during the fermentation, is keeping 1, when the concentration of ammediol is suitable, can make the molar yield of glycerine improve 4.3 to 31.5 percentage points.
The organic intermediary metabolism molecule of interpolation that proposes by the above-mentioned the present invention of experiment showed, promotes thalline to synthesize 1, and the method for ammediol when guaranteeing the thalline high yield, has significantly improved the efficient that thalline is produced product, has reduced production cost.
Add organic intermediary metabolism molecule experimental result in table 1 fermention medium
| Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Organic acid and add-on | Do not add organic acid | 0.2g/L citric acid | 0.5g/L fumaric acid | 0.7g/L succsinic acid | 0.2g/L citric acid 0.1g/L succsinic acid 0.1g/L fumaric acid | 0.23g/L citric acid 0.42g/L succsinic acid | 1.0g/L fumaric acid |
| 1, ammediol concentration, g/L | 56.2 | 54.5 | 62.1 | 61.4 | 68.2 | 58.6 | 52.7 |
| The glycerine molar yield, % | 48.9 | 52.1 | 64.3 | 59.2 | 60.5 | 54.3 | 50.9 |
Table 2 thalli growth exponential phase, added organic intermediary metabolism molecule experimental result
| Comparative example | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | |
| Organic acid and add-on | Do not add organic acid | 0.2g/L citric acid | 0.5g/L citric acid | 0.23g/L citric acid 0.42g/L succsinic acid | 0.2g/L citric acid 0.1g/L succsinic acid 0.1g/L fumaric acid | 0.2g/L citric acid 0.1g/L succsinic acid 0.1g/L oxysuccinic acid 0.1g/L fumaric acid | 1.0g/L fumaric acid |
| 1, ammediol concentration, g/L | 56.2 | 56.5 | 58.6 | 62.2 | 70.3 | 65.2 | 53.5 |
| The glycerine molar yield, % | 48.9 | 53.2 | 54.5 | 61.1 | 68.8 | 80.4 | 55.4 |
Claims (6)
1, a kind of microorganism utilizes the glycerine anaerobically fermenting to produce 1, the method of ammediol, contain the fermention medium that preparation is used to cultivate Cray Bai Shi bacillus, and in above-mentioned substratum, insert Cray Bai Shi bacillus seed culture fluid, carry out anaerobically fermenting synthetic 1, the step of ammediol is characterized in that, adding concentration in described fermention medium is organic intermediary metabolism molecule of 0.1g/L～1.0g/L.
2, method according to claim 1 is characterized in that, described organic intermediary metabolism molecule is selected from one or more in citric acid, succsinic acid, fumaric acid or the oxysuccinic acid.
3, method according to claim 1 is characterized in that, adds vitamins C and/or vitamin-E reductive agent in described fermention medium, and add-on is 40mg/L～150mg/L.
4, a kind of microorganism utilizes the glycerine anaerobically fermenting to produce 1, the method of ammediol, contain the fermention medium that preparation is used to cultivate Cray Bai Shi bacillus, and in above-mentioned substratum, insert Cray Bai Shi bacillus seed culture fluid, carry out anaerobically fermenting synthetic 1, the process of ammediol, it is characterized in that, carrying out anaerobically fermenting synthetic 1, in the process of ammediol, add organic intermediary metabolism molecule in the exponential phase of thalli growth, the concentration of described organic intermediary metabolism molecule in fermented liquid is 0.1g/L～1.0g/L.
5, method according to claim 4 is characterized in that, described organic intermediary metabolism molecule is selected from one or more in citric acid, succsinic acid, fumaric acid or the oxysuccinic acid.
6, method according to claim 4 is characterized in that, adds vitamins C and/or vitamin-E reductive agent in the exponential phase of thalli growth, and add-on is 40mg/L～150mg/L.
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| CN100467607C CN100467607C (en) | 2009-03-11 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311979A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for promoting to biosynthesize 1,3-propylene glycol by adding reducing sugar |
| CN102443608A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Method for producing 1,3-propylene glycol by using microbial fermentation |
| CN102864177A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Method for promoting fermentation of microorganism to produce 1,3-propylene glycol |
| CN105647981A (en) * | 2016-03-29 | 2016-06-08 | 南京工业大学 | Method for enhancing glycerol utilization of microbial cells through electrochemical system and application of method |
| CN106676139A (en) * | 2016-10-19 | 2017-05-17 | 大连理工大学 | Preparation method of water-soluble carbon dot and application of water-soluble carbon dot in microbial fermentation |
| CN108070622A (en) * | 2016-11-11 | 2018-05-25 | 湖南尔康制药股份有限公司 | A kind of method that biological fermentation process prepares 1,3- propylene glycol |
-
2005
- 2005-10-26 CN CNB2005100475406A patent/CN100467607C/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311979A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for promoting to biosynthesize 1,3-propylene glycol by adding reducing sugar |
| CN102311979B (en) * | 2010-07-07 | 2013-07-24 | 中国石油化工股份有限公司 | Method for promoting to biosynthesize 1,3-propylene glycol by adding reducing sugar |
| CN102443608A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Method for producing 1,3-propylene glycol by using microbial fermentation |
| CN102443608B (en) * | 2010-10-12 | 2014-01-01 | 中国石油化工股份有限公司 | Method for producing 1,3-propylene glycol by using microbial fermentation |
| CN102864177A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Method for promoting fermentation of microorganism to produce 1,3-propylene glycol |
| CN105647981A (en) * | 2016-03-29 | 2016-06-08 | 南京工业大学 | Method for enhancing glycerol utilization of microbial cells through electrochemical system and application of method |
| CN105647981B (en) * | 2016-03-29 | 2019-06-04 | 南京工业大学 | Method for enhancing glycerol utilization of microbial cells through electrochemical system and application of method |
| CN106676139A (en) * | 2016-10-19 | 2017-05-17 | 大连理工大学 | Preparation method of water-soluble carbon dot and application of water-soluble carbon dot in microbial fermentation |
| CN108070622A (en) * | 2016-11-11 | 2018-05-25 | 湖南尔康制药股份有限公司 | A kind of method that biological fermentation process prepares 1,3- propylene glycol |
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